Water can adsorb molecularly or dissociatively onto different sites of metal oxide surfaces. These adsorption sites can be disentangled using surface-sensitive vibrational spectroscopy. Here, we model Vibrational Sum Frequency (VSF) spectra for various forms of dissociated, deuterated water on a reconstructed, Al-terminated α-Al2O3(0001) surface at submonolayer coverages (the so-called 1-2, 1-4, and 1-4′ modes). Using an efficient scheme based on velocity-velocity autocorrelation functions, we go beyond previous normal mode analyses by including anharmonicity, mode coupling, and thermal surface motion in the framework of ab initio molecular dynamics. In this way, we calculate vibrational density of states curves, infrared, and VSF spectra. Comparing computed VSF spectra with measured ones, we find that relative frequencies of resonances are in quite good agreement and linewidths are reasonably well represented, while VSF intensities coincide not well. We argue that intensities are sensitively affected by local interactions and thermal fluctuations, even at such low coverage, while absolute peak positions strongly depend on the choice of the electronic structure method and on the appropriate inclusion of anharmonicity.

1.
P. A.
Cox
and
V. E.
Henrich
,
The Surface Science of Metal Oxides
(
Cambridge University Press
,
Cambridge
,
1994
).
2.
H.-J.
Freund
,
H.
Kuhlenbeck
, and
V.
Staemmler
,
Rep. Prog. Phys.
59
(
3
),
283
(
1996
).
3.
G. E.
Brown
,
V. E.
Henrich
,
W. H.
Casey
,
D. L.
Clark
,
C.
Eggleston
,
A.
Felmy
,
D. W.
Goodman
,
M.
Grätzel
,
G.
Maciel
,
M. I.
McCarthy
,
K. H.
Nealson
,
D. A.
Sverjensky
,
M. F.
Toney
, and
J. M.
Zachara
,
Chem. Rev.
99
(
1
),
77
174
(
1999
).
4.
M. A.
Henderson
,
Surf. Sci. Rep.
46
,
1
308
(
2002
).
5.
O.
Bjørneholm
,
M. H.
Hansen
,
A.
Hodgson
,
L.-M.
Liu
,
D. T.
Limmer
,
A.
Michaelides
,
P.
Pedevilla
,
J.
Rossmeisl
,
H.
Shen
,
G.
Tocci
,
E.
Tyrode
,
M.-M.
Walz
,
J.
Werner
, and
H.
Bluhm
,
Chem. Rev.
116
(
13
),
7698
7726
(
2016
).
6.
Y.
Wang
and
C.
Wöll
,
Chem. Soc. Rev.
46
(
7
),
1875
1932
(
2017
).
7.
R.
Mu
,
Z.
Zhao
,
Z.
Dohnalek
, and
J.
Gong
,
Chem. Soc. Rev.
46
(
7
),
1785
1806
(
2017
).
8.
M. E.
McBriarty
,
G. F.
von Rudorff
,
J. E.
Stubbs
,
P. J.
Eng
,
J.
Blumberger
, and
K. M.
Rosso
,
J. Am. Chem. Soc.
139
(
7
),
2581
2584
(
2017
).
9.
Z.-J.
Zhao
,
Z.
Li
,
Y.
Cui
,
H.
Zhu
,
W. F.
Schneider
,
W. N.
Delgass
,
F.
Ribeiro
, and
J.
Greeley
,
J. Catal.
345
,
157
169
(
2017
).
10.
M.-P.
Gaigeot
,
M.
Sprik
, and
M.
Sulpizi
,
J. Phys.: Condens. Matter
24
(
12
),
124106
(
2012
).
11.
K. C.
Hass
,
W. F.
Schneider
,
A.
Curioni
, and
W.
Andreoni
,
Science
282
(
5387
),
265
268
(
1998
).
12.
P.
Liu
,
T.
Kendelewicz
,
G. E.
Brown
, Jr.
,
E. J.
Nelson
, and
S. A.
Chambers
,
Surf. Sci.
417
(
1
),
53
65
(
1998
).
13.
P. J.
Eng
,
T. P.
Trainor
,
G. E.
Brown
, Jr.
,
G. A.
Waychunas
,
M.
Newville
,
S. R.
Sutton
, and
M. L.
Rivers
,
Science
288
(
5468
),
1029
1033
(
2000
).
14.
K. C.
Hass
,
W. F.
Schneider
,
A.
Curioni
, and
W.
Andreoni
,
J. Phys. Chem. B
104
(
23
),
5527
5540
(
2000
).
15.
L.
Zhang
,
C.
Tian
,
G. A.
Waychunas
, and
Y. R.
Shen
,
J. Am. Chem. Soc.
130
(
24
),
7686
7694
(
2008
).
16.
J. G.
Catalano
,
Geochim. Cosmochim. Acta
75
(
8
),
2062
2071
(
2011
).
17.
S.
Heiden
,
J.
Wirth
,
R. K.
Campen
, and
P.
Saalfrank
,
J. Phys. Chem. C
122
(
27
),
15494
15504
(
2018
).
18.
G.
Melani
,
Y.
Nagata
,
J.
Wirth
, and
P.
Saalfrank
,
J. Chem. Phys.
149
(
1
),
014707
(
2018
).
19.
N. G.
Petrik
,
P. L.
Huestis
,
J. A.
LaVerne
,
A. B.
Aleksandrov
,
T. M.
Orlando
, and
G. A.
Kimmel
,
J. Phys. Chem. C
122
(
17
),
9540
9551
(
2018
).
20.
M.
DelloStritto
,
S. M.
Piontek
,
M. L.
Klein
, and
E.
Borguet
,
J. Phys. Chem. C
122
(
37
),
21284
21294
(
2018
).
21.
S.
Heiden
,
D.
Usvyat
, and
P.
Saalfrank
,
J. Phys. Chem. C
123
(
11
),
6675
6684
(
2019
).
22.
T.
Kurita
,
K.
Uchida
, and
A.
Oshiyama
,
Phys. Rev. B
82
(
15
),
155319
(
2010
).
23.
J.
Wirth
and
P.
Saalfrank
,
J. Phys. Chem. C
116
(
51
),
26829
26840
(
2012
).
24.
H.
Kirsch
,
J.
Wirth
,
Y.
Tong
,
M.
Wolf
,
P.
Saalfrank
, and
R. K.
Campen
,
J. Phys. Chem. C
118
(
25
),
13623
13630
(
2014
).
25.
Y.
Tong
,
J.
Wirth
,
H.
Kirsch
,
M.
Wolf
,
P.
Saalfrank
, and
R. K.
Campen
,
J. Chem. Phys.
142
(
5
),
054704
(
2015
).
26.
J.
Wirth
,
H.
Kirsch
,
S.
Wlosczyk
,
Y.
Tong
,
P.
Saalfrank
, and
R. K.
Campen
,
Phys. Chem. Chem. Phys.
18
,
14822
(
2016
).
27.
S.
Heiden
,
Y.
Yue
,
H.
Kirsch
,
J.
Wirth
,
P.
Saalfrank
, and
R. K.
Campen
,
J. Phys. Chem. C
122
(
12
),
6573
6584
(
2018
).
28.
X. D.
Zhu
,
H.
Suhr
, and
Y. R.
Shen
,
Phys. Rev. B
35
,
3047
3050
(
1987
).
29.
J. F. D.
Liljeblad
and
E.
Tyrode
,
J. Phys. Chem. C
116
(
43
),
22893
22903
(
2012
).
30.
H.-F.
Wang
,
L.
Velarde
,
W.
Gan
, and
L.
Fu
,
Annu. Rev. Phys. Chem.
66
,
189
216
(
2015
).
31.
P. A.
Covert
and
D. K.
Hore
,
Annu. Rev. Phys. Chem.
67
(
1
),
233
257
(
2016
).
32.
L.
Dalstein
,
E.
Potapova
, and
E.
Tyrode
,
Phys. Chem. Chem. Phys.
19
,
10343
10349
(
2017
).
33.
M. R.
Fagiani
,
X.
Song
,
S.
Debnath
,
S.
Gewinner
,
W.
Schöllkopf
,
K. R.
Asmis
,
F. A.
Bischoff
,
F.
Müller
, and
J.
Sauer
,
J. Phys. Chem. Lett.
8
(
6
),
1272
1277
(
2017
).
34.
M.
DelloStritto
and
J.
Sofo
,
J. Phys. Chem. A
121
(
16
),
3045
3055
(
2017
).
35.
D. A.
McQuarrie
,
Statistical Mechanics
(
University Science Books
,
2000
).
36.
B. J.
Berne
and
G. D.
Harp
,
Adv. Chem. Phys.
17
,
63
227
(
1970
).
37.
A.
Perry
,
C.
Neipert
,
B.
Space
, and
P. B.
Moore
,
Chem. Rev.
106
(
4
),
1234
1258
(
2006
).
38.
Y.
Nagata
and
S.
Mukamel
,
J. Am. Chem. Soc.
132
(
18
),
6434
6442
(
2010
).
39.
J. L.
Skinner
,
P. A.
Pieniazek
, and
S. M.
Gruenbaum
,
Acc. Chem. Res.
45
(
1
),
93
100
(
2012
).
40.
M.
Sulpizi
,
M.
Salanne
,
M.
Sprik
, and
M.-P.
Gaigeot
,
J. Phys. Chem. Lett.
4
(
1
),
83
87
(
2013
).
41.
P.
Huang
,
T. A.
Pham
,
G.
Galli
, and
E.
Schwegler
,
J. Phys. Chem. C
118
(
17
),
8944
8951
(
2014
).
42.
T.
Ohto
,
K.
Usui
,
T.
Hasegawa
,
M.
Bonn
, and
Y.
Nagata
,
J. Chem. Phys.
143
(
12
),
124702
(
2015
).
43.
S.
Luber
,
J. Phys. Chem. Lett.
7
,
5183
5187
(
2016
).
44.
M.-P.
Gaigeot
and
M.
Sulpizi
,
Mineral/Water Interaction
(
John Wiley & Sons
,
2016
), pp.
271
309
.
45.
A.
Morita
and
J. T.
Hynes
,
Chem. Phys.
258
(
2
),
371
390
(
2000
).
46.
A.
Morita
and
J. T.
Hynes
,
J. Phys. Chem. B
106
(
3
),
673
685
(
2002
).
47.
T.
Ishiyama
and
A.
Morita
,
J. Phys. Chem. C
111
(
2
),
721
737
(
2007
).
48.
T.
Ishiyama
,
T.
Imamura
, and
A.
Morita
,
Chem. Rev.
114
(
17
),
8447
8470
(
2014
).
49.
T.
Ishiyama
and
A.
Morita
,
Annu. Rev. Phys. Chem.
68
(
1
),
355
377
(
2017
).
50.
R. W.
Nunes
and
X.
Gonze
,
Phys. Rev. B
63
,
155107
(
2001
).
51.
A. A.
Mostofi
,
J. R.
Yates
,
G.
Pizzi
,
Y.-S.
Lee
,
I.
Souza
,
D.
Vanderbilt
, and
N.
Marzari
,
Comput. Phys. Commun.
185
,
2309
2310
(
2014
).
52.
R.
Khatib
and
M.
Sulpizi
,
J. Phys. Chem. Lett.
8
(
6
),
1310
1314
(
2017
).
53.
S.
Hosseinpour
,
F.
Tang
,
F.
Wang
,
R. A.
Livingstone
,
S. J.
Schlegel
,
T.
Ohto
,
M.
Bonn
,
Y.
Nagata
, and
E. H. G.
Backus
,
J. Phys. Chem. Lett.
8
,
2195
2199
(
2017
).
54.
S. A.
Corcelli
and
J. L.
Skinner
,
J. Phys. Chem. A
109
(
28
),
6154
6165
(
2005
).
55.
B. M.
Auer
and
J. L.
Skinner
,
J. Chem. Phys.
128
(
22
),
224511
(
2008
).
56.
T.
Ohto
,
H.
Tada
, and
Y.
Nagata
,
Phys. Chem. Chem. Phys.
20
,
12979
12985
(
2018
).
57.
W.
Kohn
and
L. J.
Sham
,
Phys. Rev.
140
,
1133
1138
(
1965
).
58.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
(
18
),
3865
3868
(
1996
).
59.
P. E.
Blöchl
,
Phys. Rev. B
50
(
24
),
17953
17979
(
1994
).
60.
G.
Kresse
and
J.
Hafner
,
Phys. Rev. B
47
(
1
),
558
561
(
1993
).
61.
G.
Kresse
and
J.
Hafner
,
Phys. Rev. B
48
(
17
),
13115
13118
(
1993
).
62.
G.
Kresse
and
D.
Joubert
,
Phys. Rev. B
59
(
3
),
1758
1775
(
1999
).
63.
S.
Grimme
,
J. Comput. Chem.
27
(
15
),
1787
1799
(
2006
).
64.
S.
Nosé
,
Mol. Phys.
52
(
2
),
255
268
(
1984
).
65.
H.
Jónsson
,
M.
Greg
, and
K. W.
Jacobsen
,
Nudged Elastic Band Method for Finding Minimum Energy Paths of Transitions
(
World Scientific
,
1995
), pp.
385
404
.
66.
G.
Henkelman
,
B. P.
Uberuaga
, and
H.
Jónsson
,
J. Chem. Phys.
113
(
22
),
9901
9904
(
2000
).
67.
M. K.
Kesharwani
,
B.
Brauer
, and
J. M. L.
Martin
,
J. Phys. Chem. A
119
(
9
),
1701
1714
(
2015
).
68.
X.
Wei
and
Y. R.
Shen
,
Phys. Rev. Lett.
86
,
4799
4802
(
2001
).
69.
S.
Sun
,
F.
Tang
,
S.
Imoto
,
D. R.
Moberg
,
T.
Ohto
,
F.
Paesani
,
M.
Bonn
,
E. H. G.
Backus
, and
Y.
Nagata
,
Phys. Rev. Lett.
121
,
246101
(
2018
).
70.
T.
Ohto
,
M.
Dodia
,
S.
Imoto
, and
Y.
Nagata
,
J. Chem. Theory Comput.
15
(
1
),
595
602
(
2019
).
71.
X.
Zhuang
,
P. B.
Miranda
,
D.
Kim
, and
Y. R.
Shen
,
Phys. Rev. B
59
,
12632
12640
(
1999
).
You do not currently have access to this content.